CN104619637B

CN104619637B - Solid carbon product comprising CNT with and forming method thereof

Info

Publication number: CN104619637B
Application number: CN201380046917.9A
Authority: CN
Inventors: D·B·诺伊斯
Original assignee: Seerstone LLC
Current assignee: Seerstone LLC
Priority date: 2012-07-12
Filing date: 2013-07-09
Publication date: 2017-10-03
Anticipated expiration: 2033-07-09
Also published as: US9604848B2; JP2015525731A; CN107651667A; MX2015000515A; CN104619637A; HK1245754A1; JP2018111312A; WO2014011631A1; US20190322056A1; US20150225242A1; US20170197835A1; JP6284934B2

Abstract

Formed the method for solid carbon product include multiple nanotubes being arranged in forcing press and by applying heat on the multiple CNT to form the solid carbon product.It is processed further may include to sinter the solid carbon product, to form multiple covalently bound CNTs.The solid carbon product includes the hole of multiple intermediate value minimum dimensions for having and being less than about 100 nm between the CNT.Certain methods include the material of compressed package carbon nanotubes, compressed material is heated in non-reacted environment to form covalent bond between adjacent carbon nanotubes to form the solid carbon product of sintering, and the temperature that the carbon that the solid carbon product of the sintering is cooled into CNT will not be aoxidized, remove afterwards obtained by solid carbon product for being processed further, transport or use.

Description

Solid carbon product comprising CNT with and forming method thereof

Prioity claim

" the Solid of U.S. Provisional Patent Application Serial No. 61/671,022 submitted this application claims on July 12nd, 2012 Carbon Products Comprising Carbon Nanotubes and Methods of Forming Same " Shen Please day rights and interests, the disclosure of which is incorporated herein in its entirety by reference herein.

Field

The embodiment of the disclosure is related to the method and system for forming solid carbon product by CNT, the solid Carbon product includes the mixture and CNT and the mixture of other materials of different types of CNT.

Background

Each with Dallas B.Noyes name announce documents below disclose on the application background information and Each it is incorporated herein in its entirety by reference herein：

The U.S. Patent Publication number 2012/0034150A1 announced for 9 days 2 months 1.2012 years；

The international application no PCT/US2013/000071 that on March 15th, 2.2013 submits；

The international application no PCT/US2013/000072 that on March 15th, 3.2013 submits；

The international application no PCT/US2013/000073 that on March 15th, 4.2013 submits；

The international application no PCT/US2013/000075 that on March 15th, 5.2013 submits；

The international application no PCT/US2013/000076 that on March 15th, 6.2013 submits；

The international application no PCT/US2013/000077 that on March 15th, 7.2013 submits；

The international application no PCT/US2013/000078 that on March 15th, 8.2013 submits；

The international application no PCT/US2013/000079 that on March 15th, 9.2013 submits；And

The international application no PCT/US2013/000081 that on March 15th, 10.2013 submits.

Commonly relied in engineering material using CNT (" CNT ") conventional method and CNT is embedded into matrix material In material.CNT be currently use metal, plastics, thermosetting resin, epoxy resin and other materials as keep CNT together Matrix come in various composite constructions process, so as to create solid objects.The CNT is used and is made improvements material character Reinforcing material.Be using the typical purpose of CNT in the base in order to increase intensity, reduce weight or improve compound Electric conductivity and thermal conductivity.

The method of the main material being made up of CNT of manufacture includes CNT is woven into fiber and is made " Bark stone (buckyrock) ".On May 31st, 2005 authorizes and entitled " Entangled single-wall carbon The nanotube solid material and methods for making same " disclosure of U.S. Patent number 6,899,945 A kind of method for manufacturing Bark stone.Bark stone is to include three-dimensional, the solid block of material of single wall CNT entanglement networks.Bar Gram stone it is big for mechanically intensity, it is tough and tensile and shock proof, wherein bulk density is about 0.72g/cm³(referring to U.S. Patent number 6,899,945 embodiment 3).The single wall CNT of Bark stone form exists with scramble network.CNT scramble network seems logical The Van der Waals force crossed between CNT and it is held in place by by CNT physical entanglement or interference.A type of Bark Stone is slow from the slurries to remove water to generate thickener and allow the thickener very by forming CNT slurries in water Slowly dry to be made, to cause the CNT networks for maintaining the thickener during solvent evaporates.Bark stone can be used for needing tool Have in the various applications of light material of mechanical strength, toughness and impact resistance, such as system ballistic protective system.

Although the conventional material comprising CNT has interesting and useful property, these materials are constituted Single CNT has dramatically different property.Therefore, the material with property that can be more suitable with independent CNT property is produced Material is favourable.

Disclosure

Formed solid carbon product method such as extrude, be molded including pressure compaction method, roll-in, injection molding, with formation Include the solid shape of multiple CNTs.CNT is optionally mixed with other materials.Such solid shape can pass through It is heated to being enough sintering at least some CNT temperature under an inert atmosphere so that forming covalent bond between adjacent C NT to enter One step is processed.Methods described may include to form multiple nanotubes, the multiple nanotube is arranged in forcing press, and by heat Amount and pressure put on multiple CNTs to form solid carbon product.In sintering, the material of gained is with two kind or more The novel substance composition of a variety of CNT (there is covalent bond between them).

Solid carbon product is regardless of whether sinter, comprising the interlocking CNT for limiting multiple holes throughout the material.Calking The size of hole can be controlled by a variety of methods, and the feature that methods described includes the CNT that control constitutes solid carbon product is straight Footpath, be incorporated in from solid carbon product remove when can generate the other materials of hole and solid carbon product is formed under it Pressure and temperature.

The solid carbon product of sintering includes multiple covalently bound CNTs.Certain methods include compression containing carbon nanometer The material of pipe, heats compressed material to form chemical bond and shape between adjacent carbon nanotubes in non-reacted environment Into the carbon nano tube structure of combination, and combining carbon nano tube structure be cooled to the carbon of CNT will not be with oxygen reaction Temperature.

Other methods include forming solid carbon product by compressing the material containing CNT first and then will The solid carbon product of gained is positioned under sintering condition.Sintering condition may include inert environments, such as vacuum or inert atmosphere (example Such as, argon gas or helium).Solid carbon product is heated to required temperature, continued for some time, to be induced between adjacent C NT Object, is cooled to less than the aerial oxidizing temperature of carbon by covalent bond afterwards.Then can be by the product from sintering condition It is middle to remove.

Such method may include any of multiple standards industrial processing methods, such as extruding, molding, injection molding, Static pressure and roll-in.The sintering of solid carbon product can be carried out in plurality of devices, such as be usually used in the powder metallurgy and sintering of sintering Ceramic manufacturing in equipment.The sintering of solid carbon product may include any of multiple means, and the means include sensing Heating, plasma arc electric discharge, high temperature and high pressure kettle and annealing furnace and other relevant apparatus and side as known in the art Method.

Brief description

Fig. 1 to Fig. 4 is the simplification figure of CNT；

Fig. 5 to Fig. 9 is for the simplification sectional view for the forcing press for forming solid carbon product；

Figure 10 and Figure 11 are the simplification figure of the structure for the CNT for showing connection；And

Figure 12 is the figure for showing the bulk density by being compacted and sintering the solid carbon product formed.

Implement the mode of the present invention

The disclosure includes the method that solid carbon product is formed by applying pressure to CNT and for by heat Measure the method for putting on the solid product formed by such method.Solid carbon product is applicable to following various applications, such as mistake Filter, reactor, electrical component (for example, electrode, wire, battery), structure (for example, beam, frame, pipeline), fastener, the zero of molding Part (for example, gear, bushing, piston, turbine, turbo blade, engine cylinder-body) etc..Such solid carbon product can be relative to routine Material shows enhanced property (for example, intensity, electric conductivity or thermal conductivity, specific surface area, porosity etc.).The disclosure includes containing There is the class new material for the multiple CNT for being configured to solid shape under stress.When such solid shape is sintered, described CNT it is at least some between form covalent bond, so as to form solid shape.This material has numerous useful properties.

Term " sintering " as used herein means and is included in be enough between at least some adjacent C NT, at them At least some contact points between induction carbon-to-carbon covalent bond temperature and pressure under annealing or pyrolysis CNT.

Term " catalyst residue " as used herein means and including any non-carbon element relevant with CNT.This Class non-carbon element may include the nano particle of the metallic catalyst in CNT growth tip and randomly or otherwise divide Metallic atom or atomic group of the cloth on CNT and its surface.

Term " green compact " as used herein mean and including and unsintered any solid carbon product.

CNT can be formed by any method known in the art, and methods described includes arc discharge, laser ablation, hydro carbons Pyrolysis, Boudouard reaction, Bosch reaction and correlation oxidation of coal reduction reaction or wet chemical process (for example, Diels-Alder reacts).Method described herein can be applied to CNT, either what manufacture or synthetic method.

CNT can be used as single wall and many wall carbon with different-diameter of the diameter range from several nanometers to 100 nanometers or bigger Nanotube occurs.CNT can have various length and form, and can be used as substantially parallel " woods shape thing (forest) entity or " pillow thing (pillow) " of structuring aggregation ", randomly tangled occurs.CNT can also be formed or It is mixed to form the CNT's with various combination and features above distribution (number, diameter, length, form, orientation of wall etc.) Many different mixtures.Different mixtures can be produced with spy when mixing and for forming solid carbon product as described herein The product for the property not being engineered.For example, the median pore size of the interstitial air space between the CNT of composition solid carbon product is usual Characteristic diameter with the CNT for forming solid carbon product is generally proportionate.Median pore size influence solid carbon product Overall porosity and density.

Different CNT features and construction are shown into Fig. 4 in Fig. 1.Fig. 1 shows single wall CNT100, wherein carbon atom 102 with Single cylinder form links together.Into hexagoinal lattice, and therefore, formation shows as being rolled into pipe the covalent bond of carbon atom 102 The CNT 100 of the single graphite linings of form.CNT 100 can be conceptualized as " graphene film rolled " calibration grid pattern, and it is determined To cause carbon atom 102 to be spiraled with the different angles of the axis relative to CNT 100.The angle be referred to as " chirality " and Common name form include armchair shape and zigzag, such as Mildred S.Dresselhaus＆Phaedon Avouris, Introduction to Carbon Materials Research,in Carbon Nanotubes:Synthesis, Structure,Properties,and Applications,1,6(Mildred S.Dresselhaus,Gene Dresselhaus , ＆Phaedon Avouris, editor, 2001) described in, the full content of the document is by reference It is incorporated herein.Many chiralitys are all possible；Different properties can be shown (for example, CNT with different chiral CNT 100 100 can have semiconductor or metal electrical properties).

CNT 100 has the internal diameter related to the number of the carbon atom 102 in circumference cross section.CNT 100 shown in Fig. 1 With zigzag pattern, as shown in the ends of CNT 100.Diameter can also affect on CNT 100 property.Single wall CNT 100 can have There are many different diameters, such as from about 1.0nm (nanometer) to 10nm or bigger.The length that CNT 100 can have is about 10nm To about 1 μm (micron), such as from about 20nm to about 500nm or about 50nm to about 100nm.CNT 100 generally has about 100:1 to 1000:1 or bigger aspect ratio (that is, CNT length and CNT diameter ratio).

CNT with more than one wall is referred to as many wall CNT.Fig. 2 is schematically shown with generally around common axis The many wall CNT 120 for the multiple graphite linings 122,124,126,128 being disposed concentrically upon.Double-walled and three wall carbon nano tubes are retouched once in a while State as different classifications；However, they can be considered as the other many wall CNT 120 of infima species.Many wall CNT 120 diameter range can It is about 3nm to substantially exceeding 100nm.Many wall CNT120 of external diameter with about 40nm or bigger are sometimes referred to as in this area Carbon nano-fiber.

Fig. 3 shows many wall CNT 140,150 of two kinds of forms.In CNT 140, a single wall CNT 142 be arranged at compared with In the single wall CNT 144 of major diameter, the single wall CNT 144 may be disposed at the single wall CNT of another or even larger diameter again In 146.This CNT 140 is similar with the CNT 120 shown in Fig. 2, but including three rather than four single wall CNT 142,144, 146.Another form of many wall CNT illustrated in fig. 3 are CNT 150, and it can be conceptualized as being rolled into the single graphene of pipe Piece 152.

Fig. 4 schematically shows the single wall CNT 180 of the nanometer bud 182 with connection.Nanometer bud 182 has and spherical bar The similar structure of this special fullerene (buckminsterfullerene) (" buckyballs (buckyball) ") of Triprolidine Hydrochloride, and pass through Carbon-carbon bond is combined with single wall CNT 180.Structure as shown in by Fig. 4 shows, can be to single wall CNT 180 wall or to many walls CNT outer wall is modified.At binding site between nanometer bud 182 and CNT 180, carbon double bond can be destroyed and in CNT " hole " is formed in 180 wall.These holes may influence CNT 180 mechanically and electrically property.In single wall CNT, when with When unmodified cylindrical CNT is compared, these holes may introduce relative weakness.In many wall CNT, outer wall can be by shadow Ring, but any inwall may keep complete.

CNT is generally formed in this mode for growing tip for making catalyst nano-particles be embedded in CNT.This Catalyst is optionally removed by light washing (for example, by acid elution).Not by the situation of specific theoretical constraint Under, it is believed that if the catalyst retains in position, catalyst atoms are mobilized during sintering process, and can be moved Move on on the surface of CNT or in its stomata.This technique can be by catalyst atoms randomly, equably or otherwise Disperse throughout solid carbon product agglomerate and there can be significant impact to the property of solid carbon product.For example, catalyst material The ability of electric conductivity or the other chemical reactions of catalysis may be influenceed.

Catalyst granules can also be chosen to other reactions of the catalysis in addition to solid carbon is formed.Catalyst granules can be any Material, such as transition metal or its any compound or alloy.For example, catalyst granules may include nickel, vanadium oxide, palladium, platinum, gold, Ruthenium, rhodium, iridium etc..Because catalyst granules is connected to CNT or associated with CNT in addition, every kind of catalyst granules can be with it Separate its catalyst granules physics.Therefore, the surface area of catalyst granules can dissipating than the catalyst with phase homogenous quantities Package material is much bigger.It is connected to amount of the CNT catalyst granules therefore for the catalyst material required for reduction catalytic reaction And can be particularly advantageous for reduction catalyst cost.It is used as the solid carbon product of the compression of catalyst in many applications It can benefit from CNT and the catalytic activity of both metal catalyst particles being embedded in CNT growth tip.

It can be single wall CNT, many wall CNT or its combination for the CNT in methods herein, include CNT bimodal size Combination, the mixture of single wall and many wall CNT, different size of single wall CNT mixture, different size of many wall CNT mixing Thing etc..The CNT can be the form of the compound, the compound of pressure molding or dumpable liquid such as thin slice molding.Institute CNT is stated to may be disposed at forcing press or construction and configure in any other device for provide pressure to the material.The pressure Machine may include extrusion die, mould, cavity etc..

For example, in the forcing press 200 shown in Fig. 5, CNT 202 can be placed in configuration and material is carried through into extrusion die In 206 hopper 204.Forcing press 200 includes recipient 208, and it has the screw mechanism 210 for being connected to motor 212, with CNT 202 is carried across recipient 208 to extrusion die 206.Recipient 208 optionally includes being used to pass through in CNT 202 CNT 202 device is heated during recipient 208.Extrusion die 206 has an opening, and it has with staying in forcing press 200 The corresponding shape of the cross sectional shape of the part of formation.According to the shape of required object, extrusion die 206 can be replaceable.Show Some possible shape 206a, 206b, 206c of extrusion die are gone out.For example, extrusion die 206 can have be shaped like it is circular, just The opening of the shapes such as polygon, irregular polygon, I-beam.Extrusion die 206 can be configured to be formed various shapes and size The CNT of extruding object：Symmetrically or non-symmetrically, it is small to big.CNT 202 can optionally with forcing press 200 before or within Another material mixing.

In some embodiments and as shown in Fig. 6 forcing press 220, CNT 202 is placed in and is configured to material Material is transported in the hopper 224 of mould 226.Forcing press 220 includes cylinder 228, and it has the spiral for being connected to motor 232 Mechanism 230, cylinder 228 is carried across to mould 226 by CNT 202.Cylinder 228 optionally includes being used in CNT 202 By the device that CNT 202 is heated during cylinder 228.Mould 226 has an opening, and it has with staying in forcing press 220 The corresponding interior shape of the outer shape of the part of formation.According to the shape of required object, mould 226 can be replaceable. Show some possible shape 226a and 226b of mould.For example, mould 226 can have the shape of spiral or propeller. CNT202 optionally with forcing press 200 before or within another material mix, to improve mobility, release property or other Working properties.Such material then can such as be etched by suitable means, be pyrolyzed, evaporate to remove.The solid carbon production of gained Thing generally without other material and can basically comprise carbon, and include the catalysis of residual in some embodiments Agent material.

In other embodiments and as shown in Fig. 7 forcing press 240, CNT 202 is placed in and needed with restriction In the main body 244 of the interior shape of the outside of the product of formation.CNT 202 can be placed in two work surrounded by main body 244 Between plug 246,248.Main body 244, which can have, to be limited internal chamber and is configured to allow piston 246,248 slidably Wall 250.In other embodiments, single piston can be configured to abut against main body compacting CNT.

In an embodiment as shown in the forcing press 260 such as Fig. 8, CNT 202 is placed in with having to be formed The corresponding one or more surfaces of product shape mould part 262 in.One or more other quilts of mould part 264 Configuration suppresses CNT 202 to abut against mould part 262 when being suppressed by piston 266,268, as shown in Figure 9.In a word, mould Part 262,264 defines the shape of product to be formed.

Apply pressure so that CNT is configured to sticky " green compact " main body.For example, screw mechanism 210 as shown in Figure 5 and Figure 6, 230 apply pressure on CNT 202 when CNT 202 is by forcing press 200,220.Carried out by the punch die 206 shown in Fig. 5 Extruding can be continuous (product for producing endless in theory) or semi-continuous (producing many parts).The material of extruding Example includes wire rod, tubing, planform etc..Being molded as by using stiffness design in the forcing press 220 as shown in Fig. 6 (mould 226) makes the manufacturing process that flexible raw material (for example, CNT 202) shape.CNT 202 uses the shape of the mould Shape.

Piston 266,268 shown in Fig. 8 and Fig. 9 presses to CNT 202, so that CNT 202 is configured to green bodies 270. The gained green bodies 270 formed can be kept together by relatively weak power, to cause green bodies 270 easily to enter one Step shaping (for example, machining, drilling etc.), but still keep its shape in processing.The CNT of green bodies 270 can each with One or more other CNT are physically contacted with.

By applying heat in green bodies, CNT is linked together as more sticking main body, wherein at least some Adjacent CNT forms covalent bond among each other.For example, can about 1 DEG C/min to the about 50 DEG C/min rate of heat addition CNT is added Heat is at least 1500 DEG C, 1800 DEG C, 2100 DEG C, 2400 DEG C, 2500 DEG C, 2700 DEG C or is even only below the sublimation temperature of carbon (greatly About 3600 DEG C) temperature.Can also apply heat while, before or after apply pressure.For example, CNT can 10 to Suppressed under 1000MPa, such as 30MPa, 60MPa, 250MPa, 500MPa or 750Mpa.Green bodies can be passed through in the lehr The inert environments heated, such as helium or argon gas.The CNT (that is, making them be subjected to heating in oxygen-free environment) of sintering is in contact When between CNT substantially formed covalent bond.CNT sintering is typically occurred in non-oxidizing atmosphere, such as vacuum or inert atmosphere, with So that CNT will not be oxidized during sintering.Contact surface at induced chemical combine sintering CNT with green compact Material can improve the material character needed for solid structure product when comparing, such as intensity, toughness, impact resistance, electric conductivity or lead It is hot.CNT also can be in other composition as formed the metal or ceramics of composite construction, contributing to the lubricant or adhesive of processing Sintered in the presence of (for example, water, ethanol, polyvinyl alcohol, coal, tar asphalt etc.).Material can draw as powder, chip, liquid etc. Enter.Suitable metal may include such as iron, aluminium, titanium, antimony, Pasteur's metal (Babbitt metal).Suitable ceramics may include Oxide (for example, aluminum oxide, beryllium oxide, ceria, zirconium oxide etc.), carbide, boride, nitride, silicide Deng material.In it wherein there is the embodiment of the material in addition to CNT, occur covalent bond between at least some CNT, and And other material can become to be locked into CNT matrix.

CNT in the main body of sintering has the chemical bond being connected to each other.The usual chemical bond pair more stronger than physical bond CNT set assigns the property different from physical bond.That is, the main body of sintering can have the green bodies than forming it Higher intensity, thermal conductivity, electric conductivity or other properties.

, can be on CNT surface when some carbon-carbon bonds are destroyed when single wall CNT is with adjacent single wall CNT covalent bonds Hole is formed, so as to change each single wall CNT mechanically and electrically property.However, sintering single wall CNT generally such as intensity, Toughness, impact resistance, the properties of electric conductivity and thermal conductivity can still exceed unsintered single wall CNT.In many wall CNT feelings Under condition, generally only the wall of outer tube changes；And inwall keeps complete.Therefore, in such as extruding and moulding technology using many walls and The CNT of bimodal size can produce the solid structure of the property with the actual limitation for exceeding single wall CNT at many aspects.

Sintering seems to cause the formation of covalent bond at the contact point between CNT wall.That is, any given CNT can be With adjacent C NT " crosslinking " at two CNT physical contact point.Any given CNT of oversintering can be with numerous other CNT (both single wall CNT and many wall CNT) covalent bond.Which increase the intensity of resulting structures, because CNT will not be slided at binding site Move or slip off.Unsintered CNT (for example, in Bark stone) can be slided relative to each other.Because passing through being total to caused by sintering Valency is combined and may occur in which in multiple sites of CNT agglomerates, so the main body of sintering has what the Conventional aggregate than CNT was dramatically increased Intensity, toughness, impact resistance and conductibility.

Figure 10 schematically shows the cross-linked structure by sintering the two covalently bound CNT 280,282 produced.When During sintering, the covalent bonds at its contact point 284 of CNT 280,282.Each CNT can be in contact with it during sintering some Or all other CNT formation covalent bond.Due to the interior laminate layer in many wall CNT, the covalent knot between many wall CNT single wall Conjunction may occur under sintering condition.However, this covalent bond is not yet confirmed in testing.CNT is maintained in sintering process In heating and optionally pressurization, untill the cross-linking level needed for appearance.Then the CNT of sintering is cooled into CNT will not The temperature spontaneously reacted with oxygen.Hereafter, it can expose the mixture in air, to be processed further, preserve, to pack, Transport, sale etc..

In another embodiment, (for example, in oxygen, hydrogen, hydro carbons and/or another material in reactive environments In the presence of material) heating CNT mixtures.In this embodiment, heat and pressure are maintained on demand, until in reactive environments Reactant has been reacted with each other or reacted with CNT.Then the product is cooled down.In this process, reactant can in CNT shape Into other hole or stomata, so as to increase the specific surface area of the main body of sintering.Alternatively, reactant can be deposited on material Without influenceing the CNT structures of lower floor on CNT surface.

In another embodiment, initially in non-reacted environment (for example, in a vacuum, in the presence of helium or Person is in the presence of argon gas) heat and sinter CNT mixtures.After the sintering, by the heat reaction bar into suitable with pressure change Part and reactant is added in the environment.Such reactant may include various metals (as liquid or steam), metal Carbonyls, silane or hydro carbons.Reactant can fill the one of CNT lattices and reaction product each other or with the reaction of CNT carbon A little or all gaps.In some cases, such processing using other reactant can be carried out during sintering, but also may be used Individually carry out such processing.Maintain heat and pressure, until needed for appearance reaction level (crosslinking and CNT in CNT with Both reactions between reactant) untill.Then reactant mixture is cooled down and removed from reaction environment, for further Processing, preservation, packaging, transport, sale etc..

Figure 11 schematically shows covalently bound CNT 302 agglomerate 300.CNT 302 is by sintering via common Contact point 304 and other CNT 302 (many walls or single wall CNT) are combined so that aggregation be combined together into it is highly cross-linked Structure.The combination of gained can form the material with notable intensity, toughness, impact resistance and electric conductivity and thermal conductivity.

During sintering process, green bodies are collapsible, so that corresponding with the reduction of the pore-size in CNT.However, Sintering main body can due to each CNT porosity (that is, CNT center) and between CNT and within hole and remain many Hole.The main body of sintering can have intermediate value minimum dimension to be less than about 1 μm, less than about 500nm, less than about 100nm, less than about 50nm Or it is even less than about 10nm stomata or hole.That is, each hole can have measure in different directions two or more Size (for example, length, width and height, each perpendicular to one another, or diameter and length).The hole is not necessarily regular shape 's." minimum dimension " is defined as the minimum value of two or more sizes of single hole." intermediate value minimum dimension " is defined For the intermediate value of these minimum dimensions of one group of hole.

The main body sintered as described herein can be due to the hole between CNT and within CNT with high specific surface area (that is, because CNT is hollow).For example, the specific surface area of the main body of sintering can be at least about 100m²/ g, at least about 500m²/g、 At least about 750m²/ g, at least about 900m²/ g or even at least about 1000m²/g.Specific surface area can be by producing for forming solid carbon The CNT of thing characteristic diameter or diameter mixture is controlled.For example, the single wall CNT of minor diameter specific surface area is up to about 3000m²/ g, and many wall CNT of major diameter specific surface area is about 100m²/g。

Sintering main body can have high conductivity.For example, the electric conductivity of the main body of sintering can be at least about 1x 10⁵S/m (west Door every meter), at least about 1x 10⁶S/m, at least about 1x 10⁷S/m or even at least about 1x 10⁸S/m.Electric conductivity can pass through institute The quantity of gained covalent bond in the CNT types, used CNT chirality, sintering condition and the solid carbon product that use is come Control.For example, the single wall CNT with metal chiral has the electric conductivity more much higher than many wall CNT.As another example, altogether The increase of valence link number seems relevant with conductive increase.

Sintering main body can also have high-termal conductivity.For example, the thermal conductivity of the main body of sintering can be at least about 400W/mK (every meter of watt is per Kelvin), at least about at least about 1000W/mK, 2000W/mK or even at least about 4000W/mK.Institute Obtaining the thermal conductivity of solid carbon product can be controlled by used CNT type and used CNT chirality.For example, tool The single wall CNT for having metal chiral has the thermal conductivity more much higher than big many wall CNT.

Or for example, by extruding or molding CNT can be suppressed after sintering process, such as above with respect to Fig. 5 to Fig. 9 Described.In some embodiments, sintering process can for needed for the formation of object a part.For example, the section of recipient CNT can be heated to sintering temperature under an inert atmosphere, persistently cause the appropriate time amount of sintering.Such heating can be for example to feel It should heat or plasma arc heating.Therefore, it can extrude the CNT of sintering.The CNT of sintering optionally with another material such as Metal, ceramics or glass mixing.The material in very hot or extremely cold lower compacting or can be stretched across punch die.Continue for some time simultaneously And be held in place by the material for being pressed into given shape under the temperature and pressure of sintering, and be then returned to normal big Gas bar part.The product can be continuous, such as wire rod, or can be discontinuous part, such as bolt, propeller, gear.Burn (sintered or sintering) CNT of knot molding is usually directed to uses CNT (that is, with minimum impurity) in a concentrated form Material forms mouldable compound with another material such as metal.Mouldable material is placed in or is poured into rigid die In, hold it under specific temperature and pressure, and be then cooled back under ordinary atmospheric conditions.

In some embodiments, increment autofrettage can be used, wherein CNT (compression is unpressed) is placed in into non-reaction Property environment in, such as in inert gas autoclave.CNT is sintered to form covalent bond between the CNT in superficial layer and lower floor.Example Such as, laser can an a kind of pattern irradiation CNT part.Other CNT is deposited on the CNT of sintering and and then sintered.Burn Knot technique is repeated as many times as desired, to realize selected sintering CNT thickness.Then the CNT of sintering is cooled to CNT not The temperature that can be reacted with oxygen or other atmospheric gases.Then the CNT of sintering can be removed from non-reacted environment, without dirt Contaminate the CNT of sintering.In some embodiments, the cooling and from non-before the CNT of each other part is deposited by the CNT of sintering Removed in reactive environments.

In certain embodiments, the solid carbon product of sintering is formed in belt casting operation.CNT is placed on removable Dynamic takes.CNT is moved in the chamber containing non-reacted environment by the band.CNT is sintered in the chamber, then Cool down (for example, in a part of chamber) and removed from the chamber.The process can be continuously repeated, such as with formation The CNT of sintering thin slice.

In some embodiments, by electro-deposition come with the gap in another material filled solid carbon product, to enter One step handles solid carbon product.Prepare the solution for having material to be deposited.The solvent of solution can be water, organic solvent or nothing Machine solvent.Solute may include the material of such as metal salt, organic salt, metal organic salt.Electroplating solution is as known in the art And it is not described in detail herein.Pending processing solid carbon product such as by by main body immerse solution in come with it is described molten Liquid is contacted.Potential (DC voltage or alternating voltage) is put on into main body, to induce the electro-deposition of one or more solution components. Composition, potential, temperature and/or pressure are maintained, until the material of selected amount is deposited on solid carbon product.Then will be solid Body carbon product is removed and rinsed from solution, to remove excessive solution.

The solid carbon product of formation as described herein each includes the CNT of multiple crosslinkings.CNT limits multiple holes, these The intermediate value minimum dimension of hole be smaller than about 1 μm, less than about 500nm, less than about 100nm, less than about 50nm or be even less than about 10nm.Some or all of CNT can include metal, the metal for such as forming CNT metallic particles or being coated on CNT.Solid carbon Product can be structural elements (such as beam), fastener (for example, screw), moving parts (for example, propeller, bent axle), conduction Component (for example, electrode, electric wire etc.) or any other form.Solid carbon product can include another material, and it, which is scattered in, surrounds In CNT and the successive substrates being in contact with it.Solid carbon product can have the intensity improved, toughness, anti-impact compared with conventional material Hitting property and electric conductivity and thermal conductivity.

In some embodiments, solid carbon product also comprising be scattered with CNT or be otherwise fixed to CNT its The carbon of its form.For example, buckyballs may be connected to some CNT.As another example, in all or part of solid carbon product On can form one or more graphene films.

Both the solid carbon product of compression as described herein and the solid carbon product of sintering are respectively provided with various possibility Useful application.For example, the solid carbon product of compression need not realize other mechanical integrity by sintering wherein It can be used as filter, molecular sieve, catalyst and electrode in.The solid carbon product of sintering can be used for compression wherein can be used Solid carbon product application and need by sintering realize other mechanical integrity, electrical properties and other materials In the enhanced various other applications of matter.

The solid carbon product of sintering due to its mechanical integrity, absorb with high spring-constant compressive load ability with And disperse the ability of heat and can be armoring useful constituent.That is, the solid carbon product of sintering can be used for the material for forming anti-projectile Material, such as armour plate, bullet-proof vest.The solid carbon product of lightweight can be improved in mission payload, increase means of transport wheeled Journey (vehicle range) and change center of gravity.For example, the armour material of the solid carbon product comprising sintering can be beneficial to prevent There is the occupant for tilting the means of transport such as MRAP (" MRAP ") being inclined to injured and dead.Burn as described herein The solid carbon product of knot can be effective in lightweight armament system, such as mortar tube, gun barrel, barrel and other components.Sintering Solid carbon product can also be beneficial to air vehicles, such as aircraft, spaceship, guided missile.

Embodiment

Embodiment 1：The CNT of compacting sintering

CNT is formed as described in U.S. Patent Publication number 2012/0034150A1.Use 100- tons of (890-kN) pressure About 1.0 grams to 1.25 grams of CNT samples are each pressed into 15-mm diameters by machine.The sample of compacting is placed in inert gas stove (type Number 1000-3060-FP20, can be obtained from CASanta Rosa Thermal Technology, LLC) in and under vacuo Heated with 25 DEG C of speed, untill sample reaches 400 DEG C.This temperature is maintained 30 minutes, it is any to allow sample to remove Oxygen gas and water or the other materials of presence.Then inert gas (argon gas is used under more than the 3-5psi of atmospheric pressure (21 to 34kPa) Or helium) the filling stove.The stove is heated with 20 DEG C/min speed, untill sample reaches 1500 DEG C.By this temperature Maintain 30 minutes.With 5 DEG C/min continuous heatings to sintering temperature, by the residence time of this temperature maintenance 60 minutes.Then by sample Product are cooled to 1000 DEG C with 50 DEG C/min, after this, the stove are closed, untill sample reaches environment temperature.Following The sample quality, compaction pressure and sintering temperature of sample are shown in table 1.Inert gas is for the sample that is sintered at 2400 DEG C It is argon gas for helium and for other samples.

Table 1：The sample prepared in embodiment 1

Sample	Quality (g)	Compaction pressure (MPa)	Sintering temperature (DEG C)
				1	1.076	500	1800
2	1.225	750	1800
				3	1.176	250	1800
4	1.113	500	2100
				5	1.107	750	2100
6	1.147	250	2100
				7	1.103	500	2400
8	1.198	750	2400
				9	1.121	250	2400
10	1.128	250	1900
				11	1.209	500	1900
12	1.212	750	1900
				13	1.101	250	2000
14	1.091	500	2000
				15	1.225	750	2000
16	1.078	250	1700
				17	1.179	500	1700
18	1.157	750	1700

Sample 1 to 18 is harder than the sample before heating process and firmer.In 2400 DEG C of (samples of maximum sintering temperature 7 to 9) under, the bead of sintering is thinner than the sample of other sintering.The all samples prepared in embodiment 1 are qualitatively observed To be hard.

Pycnometry test display is for the sample sintered at 1800 DEG C, 2100 DEG C and 2400 DEG C, slightly coarse powder and compacting The skeletal density of thing is respectively from 2.2g/cm³It is decreased to 2.1g/cm³、2.08g/cm³And 2.05g/cm³.Bulk density is also in sintering Reduce afterwards, 1.0g/cm is decreased to less than in almost every case³.The bead thickness increase by 5% to 9% during sintering, its Middle elevated pressures compacting expands beyond lower pressure compacting.The bulk density of sample 1 to 9 is shown in table 2 and Figure 12.

Table 2：The property of the sample prepared in embodiment 1：

Embodiment 2：CNT spark plasma sintering

CNT is formed as described in U.S. Patent Publication number 2012/0034150A1.By graphite foil (from AZ Tucson Mineral Seal Corp. obtain) 2.0g to 4.0g CNT is placed in described by arrangement into the punch die of 20-mm diameters On paper tinsel.Sample is placed in spark plasma sintering (SPS) system (model SPS 25-10, from CA Santa Rosa's Thermal Technology, LLC acquisition) in.About 5Mpa axial compressive force is put on into CNT samples and then by SPS System pump down is to less than 3mTorr (0.4Pa).Sample is heated to 650 DEG C with 150 DEG C/min, and this temperature is maintained one point Clock, to allow vavuum pump to evacuate any material of degasification again.Pressure is increased to 30MPa or 57MPa compaction pressure, together When temperature with 50 DEG C/min speed is increased to 1500 DEG C.Temperature and pressure is maintained one minute.Then by temperature with 50 DEG C/ Min increases to sintering temperature, and maintains 10min or 20min.After dwelling, pressure is decreased to 5MPa, and allows sample 1000 DEG C are cooled to 150 DEG C/min, the stove is hereafter closed, untill the sample reaches environment temperature.

Sample quality, compaction pressure, compaction velocity, sintering temperature and the residence time of sample are shown in table 2 below.

Table 3：The sample prepared in embodiment 2：

The bead of the SPS sintering formed in example 2 is about 10mm thickness and has 1.3g/cm³With 1.5g/cm³It Between bulk density.In order to illustrate the intensity of these samples, sample #20 is sintered 2100 DEG C by plan, but at about 1900 DEG C, Punch die ruptures.Drift is significantly advanced, and crushes graphite punch die.After completion of testing, punch die is peeled away from sample.Sample is kept It is substantially complete, although more slightly thinner than expection.At a temperature of this can be shown that sintering is betided less than 1900 DEG C, it is small that SPS is sintered The intensity of ball is high, or even is also that so, and the sample sintered is applied for sufficiently strong with resistance in extreme temperatures Power without rupturing.

Determine the bulk density for the sample being still connected with graphite foil.For weighing about 4g's (that is, sample #21, #22 and #23) Sample, bulk density is in 1.35g/cm³With 1.50g/cm³Between.Also measure the specific insulation and conductance of sample.These numbers Shown according in table 4.Sample conductibility as graphite with the conductibility bigger than amorphous carbon and almost.

Table 4：The property of the sample prepared in embodiment 2：

Although described above containing many details, these scopes that should not be construed as limiting the invention, and only manage Solve to provide some embodiments.Similarly, the other embodiments of the present invention without departing substantially from the scope of the invention can be designed.Example Such as, the feature herein in regard to an embodiment description can also be provided in other embodiments described herein.Therefore, this hair Bright scope is only indicated and limited by appended claims and its legal equivalents rather than by described above.Belong to claim All additions of the invention as disclosed herein, deletion and modification in the connotation and scope of book are covered by the present invention.

Claims

1. a kind of method for forming solid carbon product, it includes：

Multiple CNTs comprising kish catalyst are arranged in forcing press；

10Mpa to 1000MPa pressure is put on the multiple CNT in the presence of at least one ceramics, To form the solid carbon product comprising the kish catalyst and at least one ceramic compression, at least one Ceramics are selected from the group being made up of beryllium oxide, zirconium oxide, carbide, boride and nitride；

The solid carbon product of the compression is heated to at least 2400 DEG C of temperature；With

After the solid carbon product of the compression is heated, solid carbon product is exposed to reactant gas, with reaction product The gap of filled solid carbon product, the reactant gas is selected from the group being made up of metal carbonyl, silane and hydro carbons.

2. the method as described in claim 1, it also includes sintering the CNT forming the solid carbon product of sintering.

3. method as claimed in claim 2, institute is sintered wherein sintering the CNT and being included in inert atmosphere or vacuum State CNT.

4. the method as described in claim 1, wherein setting multiple carbon nanometer comprising kish catalyst in a press Pipe, which is included in the forcing press, to be set comprising many of the metal for being selected from the group being made up of the element of periodic table the 5th race to the 10th race Individual CNT.

5. method as claimed any one in claims 1 to 3, wherein applying pressure to the multiple CNT to be formed The solid carbon product of the compression includes the solid carbon product for forming porous compression.

6. method as claimed any one in claims 1 to 3, wherein applying pressure to the multiple CNT to be formed The solid carbon product of the compression includes the solid carbon product for forming the compression of electric conductivity.

7. method as claimed in claim 6, wherein the solid carbon product for forming the compression of electric conductivity includes forming electrode.

8. method as claimed any one in claims 1 to 3, wherein applying pressure to the multiple CNT to be formed The solid carbon product of the compression includes extruding compressed solid carbon product by punch die.

9. method as claimed any one in claims 1 to 3, wherein applying pressure to the multiple CNT to be formed The solid carbon product of the compression is included in the CNT press-in die.

10. method as claimed any one in claims 1 to 3, wherein the multiple CNT is arranged in forcing press Including the multiple CNT is arranged in the mould in the forcing press.

11. method as claimed any one in claims 1 to 3, it also includes：

Prepare the liquid solution for including salt；

The solid carbon product of the compression is contacted with the liquid solution；

On the solid carbon product that potential is put on to the compression, to induce at least one component electro-deposition of the liquid solution In on the surface of the solid carbon product of the compression and formed tabular compression solid carbon product；And

The solid carbon product of the tabular compression is rinsed, therefrom to remove the liquid solution.

12. a kind of method for the carbon nano tube structure for preparing sintering, methods described includes：

It will be arranged at comprising ceramic material with the material of more than first CNT in non-reacted environment, more than first carbon Nanotube includes metal；

At least two in more than first CNT are sintered, to form covalent bond in-between, so as to form the first knot Close structure；

Another material comprising more than second CNT is set to be deposited on first integrated structure；

At least two in more than second CNT are sintered to form covalent bond in-between and sinter described first At least one in more than first CNT in integrated structure and at least one in more than second CNT It is individual, to form the second integrated structure；

Second integrated structure is cooled to the temperature less than the aerial oxidizing temperature of the CNT；And

Second integrated structure is removed from the non-reacted environment.